JP2005211818A - Adsorbent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adsorbent which can be produced easily and economically, has a wide range of options of the types of working components to be deposited and the size of molecules, and is capable of bearing a large quantity of them, and whose working components deposited are scarcely damaged. <P>SOLUTION: Silica gel satisfying the following (a) to (g) is employed: (a) a fine pore volume is 0.05 ml/g or higher and 3.0 ml/g or lower; (b) a specific surface area is 100 m<SP>2</SP>/g or higher and 1,500 m<SP>2</SP>/g or lower; (c) fine pore diameter (D<SB>max</SB>) of most frequently appearing fine pores is smaller than 35 nm; (d) the volume of the fine pores having a diameter with in a range of D<SB>max</SB>± 20% is 50% or more; (e) amorphous; (f) the total content of metal impurities is 500 ppm or less; and (g) δ satisfies the following expression (I): -0.0705×(D<SB>max</SB>)-110.36>δ wherein δ(ppm) is chemical shift of Q<SP>4</SP>peak in solid Si-NMR. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an adsorbent provided with silica gel, and more particularly to an adsorbent in which a substance that interacts with an adsorbent is supported in the pores of silica gel. The adsorbent of the present invention is, for example, a public facility such as a cafeteria, a station building, a hospital, a shopping center, a slaughterhouse, a crematorium, etc. In the manufacturing process / refining process of factories / business sites, etc., indoors such as offices, inside vehicles such as cars, trains, ships, airplanes, factories / gardens / rooftops / roads / garbage storage / compost boxes Preferably used.

  Recently, in addition to factories and business establishments for fisheries, livestock, fertilizer, agricultural chemicals, food, chemistry, etc., factories and business establishments for sewage treatment, etc. Odor sources in the area are extremely diversified, and odor pollution is a major problem. It has also been a long time since health issues related to harmful and toxic substances contained in cigarette smoke, automobile exhaust, and various gases, liquids and final products used in factories have been widely discussed.

  In view of such an object, conventionally, as one of malodor prevention techniques, a technique for adsorbing and removing malodorous substances and harmful (toxic) substances using an adsorbent has been used. Adsorbents include inorganic adsorbents typified by specific metal compounds such as activated carbon, silica, zeolite, and zinc oxide; cyclodextrins, ion exchange resins, synthetic adsorbents, liquid paraffin, ethylene glycol, propylene glycol, polyethylene glycol Organic adsorbents such as polypropylene glycol and other higher alcohols; organometallic adsorbents such as zinc ricinoleate and zinc 2-ethylhexanoate are known.

Among these, activated carbon, for example, exhibits excellent adsorption effects on olefins such as ethylene, alcohols, organic solvents such as benzene, hydrogen sulfide, mercaptans, toxic heavy metal substances, etc., but against ammonia and amines. Has the disadvantage of poor adsorption capacity.
In addition, although ion exchange resins exhibit an adsorption effect on a wide range of odorous substances and harmful substances such as hydrogen sulfide and ammonia, they have drawbacks such as being expensive and requiring time for regeneration.
In contrast, silica is suitable for use as an adsorbent because it exhibits a high adsorption effect on a wide range of substances, is excellent in cost, and does not require complicated operations such as regeneration and is easy to handle. ing.

  By the way, in recent years, in addition to adsorbents with higher functionality by adding masking agents such as fragrances to rapid physical adsorbability by porous adsorbents such as silica, deodorization by chemical adsorption ability and chemical reaction・ Many highly functional adsorbents that combine substance conversion ability have been developed. Specifically, substances that adsorb adsorbents chemically and deodorize them (organic substances, metal compounds, etc. that can interact with adsorbates via covalent bonds, ionic bonds, coordination bonds, hydrogen bonds, etc.) Or substances that cause some kind of interaction with the adsorbed material (such as photocatalyst and other oxidative decomposition components) that cause a chemical reaction with the adsorbed material and convert it to another material Hereinafter, an adsorbent in which “active component” is appropriately supported in the pores of a porous carrier such as silica can be used. The following are mentioned as a specific example of the technique regarding such a highly functional adsorbent.

Patent Document 1 discloses a technique for adsorbing and removing ammonia and amines by supporting a transition element compound such as CuSO _{4 on} porous silica having mesopores and forming a complex with ammonia and amines. It is disclosed.

Patent Document 2 discloses a technique in which fine porous inorganic powder such as silica is impregnated with a deodorant such as chlorophyll derivative, flavonoid derivative and catechin, and an antibacterial agent such as phytoncide and bamboo extract.
Patent Document 3 discloses a technique in which an N-vinylacetamide copolymer, which is an organic polymer gel, contains an aromatic / deodorant component such as a flavonoid or zinc stearate.
Patent Document 4 discloses a technique of encapsulating a deodorizing component containing a natural extract from tea, rice cake, persimmon, shiso, etc. in inorganic porous fine particles such as silica.
Patent Document 5 discloses a technique for deodorizing bad odors derived from microorganisms by supporting various deodorizing components on a porous retaining agent made of an inorganic material such as silica or an organic polymer material such as sugar or dietary fiber. Yes.

Japanese Patent Laid-Open No. 10-314577 Japanese Patent Laid-Open No. 11-246897 JP 2002-80681 A JP 2002-85543 A JP 2002-263178 A

However, when various organic polymer materials are used as a porous carrier as in the techniques described in Patent Documents 3 and 5, the strength as a carrier is not sufficient, and water resistance, heat resistance, and long-term physical property stability There was also a problem in terms of etc.
In addition, when a conventional inorganic material such as silica is used as the porous carrier as in the techniques described in Patent Documents 1, 2, 4, and 5, the active component supported under the influence of a small amount of impurities contained in the carrier. May be decomposed or denatured. In addition, there are many cases where it is costly to increase the functionality for controlling the adsorption performance of the carrier.

  From the above background, it is an adsorbent with a porous carrier that is easy and inexpensive to produce, has a wide range of choices for the types of active ingredients that can be supported and the size of the molecules, and can support a large amount of these. In addition, there has been a demand for an excellent adsorbent that does not damage the active component to be carried and that is also excellent in terms of water resistance, heat resistance, long-term physical property stability, and the like.

  The present invention has been made in view of the above-described problems. That is, the object of the present invention is an adsorbent having a porous carrier, which is easy and inexpensive to produce, has a wide range of choices with respect to the type of active ingredient to be supported and the size of its molecule, It is possible to provide an excellent adsorbent that is capable of being supported on the surface, is less likely to be damaged by the active component, and is good in terms of water resistance, heat resistance, and long-term physical property stability. .

  Therefore, as a result of intensive studies to solve the above problems, the present inventors have used a silica gel having a sharp pore distribution, a high purity, a homogeneous structure, and a low distortion as a carrier silica gel. The present inventors have found that the above problems can be effectively solved, and have completed the present invention.

That is, the gist of the present invention resides in an adsorbent characterized by comprising silica gel satisfying the following (a) to (g).
(A) The pore volume is 0.05 ml / g or more and 3.0 ml / g or less.
(B) The specific surface area is 100 m ² / g or more and 1500 m ² / g or less.
(C) The most frequent pore diameter (D _max ) is less than 35 nm.
(D) The volume of pores having a diameter in the range of D _max ± 20% is 50% or more of the total pore volume.
(E) It is amorphous.
(F) The total content of metal impurities is 500 ppm or less.
(G) When the chemical shift of the Q ⁴ peak in solid Si-NMR is δ (ppm), δ satisfies the following formula (I).
−0.0705 × (D _max ) −11.36> δ Formula (I)

  The silica used as the porous carrier of the adsorbent of the present invention is easier and cheaper to produce than the conventional carrier silica gel, and has a wide range of choices for the types of active ingredients that can be carried and the size of the molecules. It is wide and can carry a large amount of these. In addition, since the impurity metal content is low and the purity is high, there is little risk of damaging the supported active ingredient. In addition, it is excellent in water resistance, heat resistance, long-term physical property stability, and the like.

  Therefore, the adsorbent of the present invention obtained by using it is easier and cheaper to produce than conventional adsorbents, and has a range of choices for the types of active ingredients that can be supported and the size of the molecules. It is wide and can carry a large amount of these. In addition, the adsorption performance can be controlled more precisely, and a stable adsorption effect can be obtained over a long period of time.

  Hereinafter, typical embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made without departing from the spirit of the present invention.

The adsorbent of the present invention has porous silica gel, and adsorbs a substance to be adsorbed (adsorbed object) into the pores of the silica gel. Usually, this silica gel is used as a carrier and a substance (active component) that causes some kind of interaction with an adsorbed substance is supported.
First, the silica gel used for the adsorbent of the present invention (hereinafter abbreviated as “the carrier silica gel of the present invention”) will be described.

First, the carrier silica gel of the present invention is characterized in that the pore volume and the specific surface area are in the following ranges. Specifically, the value of the pore volume is usually 0.05 ml / g or more, preferably 0.6 ml / g or more, and usually 3.0 ml / g or less, preferably 2.0 ml / g or less. The value of the surface area is usually 100 m ² / g or more, preferably 300 m ² / g or more, and usually 1500 m ² / g or less, preferably 1000 m ² / g or less, more preferably 900 m ² / g or less. To do. These pore volume and specific surface area values are measured by the BET method by nitrogen gas adsorption / desorption.

The carrier silica gel of the present invention is characterized in that the most frequent pore diameter (D _max ) is less than 35 nm. The mode pore diameter (D _max ) is a characteristic relating to the adsorption and absorption of gas and liquid, and the adsorption and absorption performance is higher as the mode pore diameter (D _max ) is smaller. Therefore, the mode pore diameter (D _max ) among various properties is an important physical property particularly for a catalyst carrier, a drug carrier, and a silica gel used as an adsorbent as in the present invention. The preferred mode pore diameter (D _max ) of the carrier silica gel of the present invention is 20 nm or less, more preferably 18 nm or less. Moreover, although a minimum in particular is not restrict | limited, Usually, it is 1 nm or more.

The most frequent pore diameter (D _max ) is determined from the isothermal desorption curve measured by the BET method by nitrogen gas adsorption / desorption, from EP Barrett, LG Joyner, PH Haklenda, J. Amer. Chem. Soc., Vol. , 373 (1951), the pore distribution curve calculated by the BJH method is plotted. Here, the pore distribution curve means the differential pore volume, that is, the differential nitrogen gas adsorption amount (ΔV / Δ (logd)) with respect to the pore diameter d (nm). Said V represents nitrogen gas adsorption volume.

Furthermore, the carrier silica gel of the present invention has a pore volume having a diameter within a range of ± 20% centered on the value of the most frequent pore diameter (D _max ) as a ratio value to the total pore volume, It is usually 50% or more, preferably 60% or more. This means that the pore diameters of the carrier silica gel of the present invention are uniform around the most frequent pore diameter (D _max ). The upper limit of the volume ratio of pores having a diameter within the range of ± 20% of the value of the most frequent pore diameter (D _max ) is not particularly limited, but is usually 90% or less with respect to the total pore volume. is there.

In relation to such characteristics, the carrier silica gel of the present invention has a differential pore volume ΔV / Δ (logd) at the most frequent pore diameter (D _max ) calculated by the BJH method of usually 2 ml / g or more, It is preferably 5 ml / g or more, and usually 20 ml / g or less, preferably 12 ml / g or less (in the above formula, d represents the pore diameter (nm) and V represents the nitrogen gas adsorption volume). . When the differential pore volume ΔV / Δ (logd) is included in the above range, it can be said that the absolute amount of pores having diameters in the vicinity of the most frequent pore diameter (D _max ) is extremely large.

  In addition, the carrier silica gel of the present invention is characterized by being amorphous, that is, no crystalline structure is observed in view of its three-dimensional structure. This means that when the carrier silica gel of the present invention is analyzed by X-ray diffraction, substantially no crystalline peak is observed. In the present specification, crystalline silica gel refers to a crystalline silica having a peak of at least one crystal structure at a position exceeding 0.6 nm (d-spacing) in an X-ray diffraction pattern. Examples of the silica gel having a crystalline structure include the aforementioned micelle template silica. Amorphous silica gel is extremely excellent in productivity as compared with crystalline silica gel.

  In addition, the carrier silica gel of the present invention is characterized by a very low impurity content and extremely high purity. Specifically, the group consisting of alkali metals, alkaline earth metals, groups 13, 14 and 15 of the periodic table, and transition metals, which are known to affect their physical properties by being present in silica gel. The total content of metal elements (metal impurities) belonging to is usually 500 ppm or less, preferably 100 ppm or less, more preferably 50 ppm or less, and most preferably 30 ppm or less. Such a small influence of impurities is one of the major factors that allow the carrier silica gel of the present invention to exhibit excellent properties such as high heat resistance and water resistance.

Furthermore, the carrier silica gel of the present invention is characterized in that its structure is less distorted. Here, the structural strain of silica gel can be expressed by the value of the chemical shift of the Q ⁴ peak in the solid-state Si-NMR measurement. Hereinafter, the relationship between the structural distortion of silica gel and the chemical shift value of the Q ⁴ peak will be described in detail.

The carrier silica gel of the present invention is a hydrate of amorphous silicic acid, and is represented by the SiO ₂ · nH ₂ O characteristic formula, but structurally, O is bonded to each vertex of the Si tetrahedron. Further, Si is further bonded to these Os to have a structure spread in a net shape. In some repeating units of Si—O—Si—O—, some of O is substituted with other members (for example, —H, —CH _3, etc.). As shown in the following formula (A), there are Si (Q ⁴ ) having ⁴ —OSi, Si (Q ³ ) having 3 —OSi as shown in the following formula (B), etc. In the formulas (A) and (B), the tetrahedral structure is ignored and the Si—O net structure is represented in a plane). In the solid Si-NMR measurement, the peaks based on the respective Si are called Q ⁴ peak, Q ³ peak,.

The carrier silica gel of the present invention is characterized in that δ satisfies the following formula (I) when the chemical shift of the Q ⁴ peak is δ (ppm).
−0.0705 × D _max −110.36> δ Formula (I)

In the conventional silica gel, the chemical shift value δ of the Q ⁴ peak is generally larger than the value calculated based on the left side of the formula (I). Therefore, the carrier silica gel of the present invention has a smaller value of the chemical shift of the Q ⁴ peak as compared with the conventional silica gel. This is nothing but the fact that the chemical shift of the Q ⁴ peak exists in a higher magnetic field in the carrier silica gel of the present invention, and as a result, the bond angle represented by two —OSi with respect to Si is more uniform. Which means less structural distortion.

In the carrier silica gel of the present invention, the chemical shift δ of the Q ⁴ peak is preferably 0.05 than the value calculated based on the left side of the formula (I) (−0.0705 × D _max −110.36). % Or less, more preferably 0.1%, particularly preferably 0.15% or more. Usually, the minimum value of the Q ⁴ peak of silica gel is −113 ppm.

The relationship between the excellent heat resistance and water resistance of the carrier silica gel of the present invention and the structural strain as described above is not necessarily clear, but is estimated as follows. In other words, silica gel is composed of aggregates of spherical particles of different sizes, but in a state where there is little structural distortion as described above, high microstructural homogeneity of the entire spherical particles is maintained. As a result, it is considered that excellent heat resistance and water resistance are exhibited. In addition, since the peak of Q ³ or less is limited in the spread of the Si—O net structure, the structural distortion of silica gel hardly occurs.

In relation to the above characteristics, the carrier silica gel of the present invention preferably has a Q ⁴ / Q ³ value of 1.3 or more, preferably 1.5 or more, as determined by solid Si-NMR measurement. Here, the value of Q ⁴ / Q ³ is the mole of Si (Q ⁴ ) in which four —OSi are bonded to Si (Q ³ ) in which three —OSi are bonded in the above-described repeating unit of silica gel. Means ratio. In general, it is known that the higher this value, the higher the thermal stability of the silica gel. From this, it can be seen that the carrier silica gel of the present invention is extremely excellent in thermal stability. On the other hand, the above-mentioned micellar template silica which is crystalline often has a Q ⁴ / Q ³ value of less than 1.3 and has low heat resistance.

The value of chemical shift and Q ⁴ / Q ³ of Q ⁴ peak, performs solid Si-NMR measurement using the method described later in the description of embodiments, it can be calculated based on the result. Further, analysis of measurement data (determination of peak position) is performed by a method of dividing and extracting each peak by, for example, waveform separation analysis using a Gaussian function.

  Unlike the conventional sol-gel method, the carrier silica gel of the present invention is hydrolyzed / condensed to form a silica hydrogel through a condensation step of condensing the silica hydrosol obtained together with a hydrolysis step of hydrolyzing silicon alkoxide. Subsequent to the hydrolysis step and the hydrolysis / condensation step, the method can be produced by a method including both a physical property adjusting step for obtaining a silica gel having a desired physical property range by hydrothermal treatment without aging the silica hydrogel.

  The silicon alkoxide used as a raw material for the carrier silica gel of the present invention includes lower alkyl groups having 1 to 4 carbon atoms such as trimethoxysilane, tetramethoxysilane, triethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. And tri- or tetraalkoxysilanes or oligomers thereof are preferable, and tetramethoxysilane, tetraethoxysilane and oligomers thereof are preferable. Since the above silicon alkoxide can be easily purified by distillation, it is suitable as a raw material for high-purity silica gel. The total content of metal impurities in the silicon alkoxide is usually 100 ppm or less, preferably 50 ppm or less, more preferably 30 ppm or less, and particularly preferably 10 ppm or less. The content rate of these metal impurities can be measured by the same method as the measurement method of the impurity content rate in general silica gel.

  The hydrolysis of the silicon alkoxide is usually 2 mol or more, preferably 3 mol or more, particularly preferably 4 mol or more, and usually 20 mol or less, preferably 10 mol or less, particularly preferably 8 mol per mol of silicon alkoxide. Performed with less than a mole of water. Hydrolysis of silicon alkoxide produces silica hydrogel and alcohol. This hydrolysis reaction is usually from room temperature to about 100 ° C., but can be performed at a higher temperature by maintaining the liquid phase under pressure. Moreover, you may add solvents, such as alcohol compatible with water, as needed at the time of a hydrolysis. Specifically, lower alcohols having 1 to 3 carbon atoms, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran, methyl cellolbu, ethyl cellolb, methyl ethyl ketone, and other organic solvents that can be arbitrarily mixed with water can be arbitrarily used. Among them, those that do not show strong acidity or basicity are preferred because they can produce a uniform silica hydrogel.

  When these solvents are not used, the stirring speed at the time of hydrolysis is particularly important for the production of the carrier silica gel of the present invention. That is, since silicon alkoxide and water for hydrolysis are separated at the initial stage, they are emulsified by stirring to promote the reaction. The stirring speed at this time is usually 30 rpm or more, preferably 50 rpm or more. If such a condition is not satisfied, it becomes difficult to obtain the carrier silica gel of the present invention. In addition, after alcohol produces | generates by hydrolysis and a liquid turns into a uniform liquid and heat_generation | fever stops, it is preferable to stop stirring in order to form a uniform hydrogel.

  Silica gel with a crystal structure tends to have poor thermal stability in water, and gels are easy to hydrolyze silicon alkoxide in the presence of a template such as a surfactant used to form pores in the gel. Includes a crystal structure. Therefore, in the present invention, it is preferable to perform the hydrolysis in the absence of a template such as a surfactant, that is, in a condition where there is no such an amount that it functions as a template.

  The reaction time depends on the reaction solution composition (type of silicon alkoxide and molar ratio with water) and the reaction temperature, and the time until gelation differs, so it is not unconditionally specified. In addition, hydrolysis can be accelerated | stimulated by adding an acid, an alkali, salts, etc. to a reaction system as a catalyst. However, the use of such an additive is not preferable in the production of the carrier silica gel of the present invention because it causes aging of the produced hydrogel, as will be described later.

  In the above silicon alkoxide hydrolysis reaction, the silicon alkoxide is hydrolyzed to produce a silicate. Subsequently, a condensation reaction of the silicate occurs, the viscosity of the reaction solution rises, and finally gelates to form a silica hydrogel. Become. In order to produce the carrier silica gel of the present invention, it is important to immediately perform a hydrothermal treatment without substantially aging so that the hardness of the hydrogel of silica produced by the above hydrolysis does not increase. Hydrolysis of silicon alkoxide produces a soft silica hydrogel. This hydrogel is stably aged or dried, and then hydrothermally treated, finally resulting in silica gel with controlled pore properties. In this method, it is not possible to produce a carrier silica gel having a physical property range defined in the present invention.

  The hydrothermal treatment of the silica hydrogel formed by hydrolysis, as described above, is performed immediately without substantially aging. This means that the soft state immediately after the formation of the silica hydrogel is maintained and the following conditions are maintained. It means to be subjected to hydrothermal treatment. It is not preferable to add acid, alkali, salt, or the like to the silicon alkoxide hydrolysis reaction system, or to make the temperature of the hydrolysis reaction too strict, since the aging of the hydrogel proceeds. In addition, the temperature and time should not be increased more than necessary in washing, drying, and leaving in post-treatment after hydrolysis.

  As means for specifically confirming the aging state of the hydrogel, the hardness of the hydrogel can be referred to. That is, a carrier silica gel having a physical property range defined by the present invention can be obtained by hydrothermally treating a soft hydrogel having a fracture stress of usually 6 MPa or less, preferably 3 MPa or less, more preferably 2 MPa or less.

  As conditions for this hydrothermal treatment, the state of water may be either liquid or gas, and it may be diluted with a solvent or other gas, but preferably liquid water is used. It is usually 0.1 times by weight or more, preferably 0.5 times by weight or more, particularly preferably 1 by weight or more, and usually 10 times by weight or less, preferably 5 times by weight or less, particularly preferably to silica hydrogel. Water in the range of 3 times by weight or less is added to form a slurry, which is usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 250 ° C. or lower, preferably 200 ° C. or lower, usually 0.1 hour or longer, preferably Is carried out in the range of 1 hour or longer, usually 100 hours or shorter, preferably 10 hours or shorter. The water used for the hydrothermal treatment may contain lower alcohols, methanol, ethanol, propanol, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and other organic solvents. The hydrothermal treatment method is also applied to a material in which silica gel is formed in a film or layer on a substrate such as particles, a substrate, or a tube. Although it is possible to perform hydrothermal treatment by changing the temperature condition using a hydrolysis reaction reactor, the optimum conditions are usually different between the hydrolysis reaction and the subsequent hydrothermal treatment. Thus, it is generally difficult to obtain the carrier silica gel of the present invention.

  When the temperature is increased under the hydrothermal treatment conditions described above, the pore diameter and pore volume of the resulting silica gel tend to increase. The hydrothermal treatment temperature is preferably in the range of usually 100 ° C. or higher and usually 200 ° C. or lower. Further, with the treatment time, the specific surface area of the silica gel obtained tends to decrease gradually after reaching the maximum once. Based on the above tendency, it is necessary to appropriately select the conditions according to the desired physical property values, but since hydrothermal treatment is intended to change the physical properties of silica gel, it is usually at a higher temperature than the hydrolysis reaction conditions described above. It is preferable to do.

If the hydrothermal treatment temperature and time are set outside the above ranges, it will be difficult to obtain the carrier silica gel of the present invention. For example, if the hydrothermal treatment temperature is too high, the pore diameter and pore volume of the silica gel become too large, and the pore distribution is also widened. On the other hand, if the hydrothermal treatment temperature is too low, the resulting silica gel has a low degree of crosslinking, poor thermal stability, no peaks in the pore distribution, or Q ⁴ / the value of Q ³ may become extremely small.

  When the hydrothermal treatment is performed in ammonia water, the same effect can be obtained at a lower temperature than in pure water. In addition, when hydrothermal treatment is performed in ammonia water, the silica gel finally obtained is generally hydrophobic as compared with the case of treatment in pure water, but usually 30 ° C. or higher, preferably 40 ° C. or higher, usually 250 ° C. or lower. In particular, when the hydrothermal treatment is performed at a relatively high temperature of 200 ° C. or less, the hydrophobicity becomes particularly high. The ammonia concentration here is preferably 0.001% or more, particularly preferably 0.005% or more, and preferably 10% or less, particularly preferably 5% or less.

  The hydrothermally treated silica hydrogel is usually dried at 40 ° C. or higher, preferably 60 ° C. or higher, usually 200 ° C. or lower, preferably 120 ° C. or lower. The drying method is not particularly limited, and it may be a batch type or a continuous type, and can be dried under normal pressure or reduced pressure. If necessary, when a carbon component derived from the raw material silicon alkoxide is contained, it can be removed usually by baking at 400 ° C. or more and 600 ° C. or less. Moreover, in order to control a surface state, it may bake at the temperature of a maximum of 900 degreeC.

  The carrier silica gel of the present invention can be obtained by pulverizing and / or classifying the dried (or baked) silica gel by various known methods as necessary. If necessary, the silica gel after pulverization and / or classification is formed by various known methods (for example, formed into a spherical shape, a tablet shape, an extruded product, a pellet shape, etc.), and this is used as the carrier of the present invention. It is also preferred to use as silica gel.

  The shape of the carrier silica gel of the present invention is not particularly limited, and can be appropriately selected from various shapes such as a powder, a granule, a sphere, a fine powder aggregate, and a molded body using the fine powder, depending on the application. The presence / absence and conditions of the above-described pulverization, classification, molding, and the like may be appropriately determined according to the selected shape.

  The carrier silica gel of the present invention has a sharper pore distribution and can control the pore diameter more precisely than a conventional porous carrier such as silica gel. Therefore, when used as an adsorbent, the pore diameter can be precisely controlled according to the molecular size of various substances (supported components: active components) to be supported in the pores. There is a wide range of choices for the size of the molecule. In addition, by appropriately controlling the pore diameter according to the molecular size of various substances to be supported in the pores (supported component: active component), it is possible to adsorb the object to be adsorbed at a stable rate. It is expected that the amount of additives commonly used to control the adsorption rate can be reduced. In addition, because of the high quality reproducibility such as pore characteristics, adsorbent products with high safety and stable quality can be obtained even in the field of high performance adsorbents where the amount of adsorption and the fluctuation speed of adsorption speed are extremely problematic. It becomes possible to provide.

  In addition, the carrier silica gel of the present invention has a very high purity, a pore wall that is relatively thick, and a homogeneous and stable structure with little distortion of the siloxane bond angle. It has the feature that there is little change in physical properties such as characteristics. Therefore, it is superior in various physical properties such as heat resistance and water resistance as compared to conventional porous carriers such as silica gel, and is used under long-term use conditions in factories and at high temperatures when added to polymer materials. These various physical properties are considered to be stably maintained even when used under severe conditions such as processing, or when a substance having high reactivity and easily deteriorating the carrier is used in combination. Moreover, since it is very high purity, it does not show unnecessary activity with respect to the active ingredient which is a supported ingredient, and it is expected that various active ingredients can be stably supported.

  Furthermore, the carrier silica gel of the present invention has a relatively high specific surface area and a high pore volume, compared with the conventional porous carrier having the same pore diameter, so that the capacity capable of carrying the active ingredient is high. In addition to being larger and capable of supporting a large amount of these, the holding ability of the active ingredient is more excellent. Thus, it is considered that the active ingredient can be used stably and effectively over a long period of time. In addition, since it is non-crystalline, production is easy and the price can be kept low.

  Furthermore, the carrier silica gel of the present invention converts a part or all of the remaining hydroxyl groups into a group containing S or N by a coupling treatment, and uses this effectively to make a more highly functional carrier. be able to.

  Because of having the various advantages listed above, the carrier silica gel of the present invention can be used by supporting various active ingredients that can be used in various situations, whether indoors, outdoors, or in vehicles. It can be suitably used as a high-performance adsorbent.

  When an active ingredient is supported on the carrier silica gel of the present invention and used as an adsorbent (adsorbent of the present invention), the active ingredient can be freely selected according to the application. Specifically, dithio-2,2-bis (benzmethylamide), 1,2-benzisothiazolin-3-one, flavonol, flavone, flavanone, diosmethine, diosmine, erodidictin, eriodictyol, hesperidin, hesperetin, chem Organic compounds such as ferrol, naringenin, naringin, quercetin, rutin, etc., and compound species having any metal element of Cu, Zn, Sn, Pb, Ti, Zr, Al, and Fe, preferably zinc oxide, ricinol Compounds such as zinc acid, zinc 2-ethylhexanoate, zinc stearate, copper sulfate and ferrous sulfate are preferably used. Naturally extracted substances include, for example, Japanese cypress, Japanese cypress, fern, bay, jasmine, cinnamon, clove, eucalyptus, bergamot, dokudami, abies, bamboo, bamboo shoots, cypress, hiba, pine, bamboo shoots, rose, holly At least one plant selected from citrus fruits such as moksei, porcupine, drill, konara, forsythia, lilac, orange, lemon, and kumquat, peppermint, apple, persimmon, plum, peach, radish, silkworm, persimmon, perilla, and aloe These may be included, and any of these may be used alone or in appropriate combination of two or more.

  Moreover, when specializing in the field | area of utilization called deodorizing, a fragrance | flavor component can also be used together as a masking agent. In this case, examples of the fragrance component include hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons, and aromatic hydrocarbons; alcohols such as aliphatic alcohols, terpene alcohols, and aromatic alcohols; aliphatic ethers, aromatics Ethers such as ethers; Oxides such as aliphatic oxides and terpene oxides; Aldehydes such as aliphatic aldehydes, thioaldehydes and aromatic aldehydes; Aliphatic ketones, terpene ketones, hydrogenated aromatic ketones, aliphatic cyclics Ketones such as ketones, non-benzene aromatic ketones, aromatic ketones; acetals; ketals; phenols; phenol ethers; fatty acids, terpene carboxylic acids, hydrogenated aromatic carboxylic acids, aromatic carboxylic acids, etc. Acids; Acid amides; Aliphatic lactones, cyclic lactones, terpene lactos Lactones such as hydrogenated aromatic lactones and aromatic lactones; esters such as aliphatic esters, furan carboxylic acid esters, aliphatic cyclic carboxylic acid esters, and aromatic carboxylic acid esters; nitromusks, nitriles, amines Synthetic fragrances such as nitrogen-containing compounds such as pyridines, quinolines, pyrrole and indole, natural fragrances from animals and plants, blended fragrances containing natural fragrances and / or synthetic fragrances, and the like. In addition, when the perfume ingredients are classified according to their functionality (function), specific examples include, for example, perfume that refreshes the mood such as peppermint, petit grain, citronella, spearmint, lime, mandarin, benzoic acid, geranium, frankincense, sandalwood Relaxing fragrances such as marjoram, lavender, labandin, sweet oranges, German camomile, roman camomile, linden, etc. , Angie Elica Root, Star Anise, Tarragon, Sassafras, and other fragrances that make you feel vibrant and dynamic, Ylang Ylang, Bitter Orange, Jasmine, Dama Close, Chai Rose, vetiver, tuberose, violet leaf, almond bitter, vanilla, balsam and other fragrances that help improve mood, basil, rosemary, laurel and other fragrances that help improve concentration, cypress, camphor, bergamot, eucalyptus, rose Examples include fragrances having an air fresh effect such as wood, near uri, cedar leaf, and cinnamon leaf, and fragrances such as kalamas root, oris root, green herb, and floral. Also regarding these fragrance | flavor components, 1 type may be used independently and 2 or more types may be used together suitably.

  In addition to these, functional substances having antibacterial properties such as hiba oil, moon peach oil, penny royal, lemongrass, lemon, spice lavender, nutmeg, oregano, sage, ginger, savory, thyme, allspice, By using cedarwood, cinnamon bark, clovebuds, caybute, pine, tea tree, capsaicin, squalene, squalane, hyaluronic acid compounds, various vitamins, etc., functions such as antibacterial properties and the like can also be imparted.

  Furthermore, in converting some or all of the hydroxyl groups remaining on the silica gel into a group containing S or N by a coupling treatment, for example, 3-mercaptopropyltrialkoxysilane, 3-aminopropyltrialkoxysilane It is preferable to treat the carrier silica gel with N-phenyl-3-aminopropyltrialkoxysilane or the like. Moreover, it is also possible to convert the S-containing group or N-containing group once supported by such treatment into a functional group having higher adsorption performance by functional group conversion. Can be granted.

  However, the components and treatment methods listed above are merely examples, and the components and treatment methods that can be supported on the carrier silica gel of the present invention are not limited thereto.

  The state in which the above-mentioned various active ingredients are supported in the pores of the carrier silica gel of the present invention may be solid or liquid, and may be a solution or a solution dissolved or dispersed in water, a solvent, a dispersion medium, or the like. Any state such as dispersed liquid may be used. Further, these active ingredients may be water-soluble or oil-soluble.

  There is no limitation on the loading method of these active ingredients, and any method can be used. Examples of such methods include the following. These method examples may be used alone or in appropriate combination.

i). A method in which the active ingredient to be supported is sealed in a container, heated to gasify the functional molecule, the carrier silica gel of the present invention is exposed to this gas, and the active ingredient is adsorbed in the pores.

ii). A method in which an active ingredient is heated and melted, and the carrier silica gel of the present invention is immersed in the melt to impregnate a fragrance or the like.

iii). A method of dissolving an active ingredient or the like in a solvent, immersing the carrier silica gel of the present invention in the solution to impregnate a perfume ingredient or the like in pores, and then evaporating the solvent.

iv). In addition, after mixing the carrier silica gel of the present invention and the active ingredient in an appropriate amount ratio, the mixture is heated to a melting point or higher of the active ingredient, etc. A method of synthesizing active components in pores by heating or the like after impregnation.

  After the impregnation treatment as described above, the surface of the carrier silica gel of the present invention is further covered with a polymer film, dextrin, etc., so that it is possible to expect the improvement of the selectivity of the adsorbent component and the adjustment of the adsorption rate. . On the other hand, when the concentration of the active ingredient (active ingredient) in the adsorbent produced by the above process is too high, it may be increased with an inexpensive powder or binder such as clay or silica gel.

  Furthermore, you may use together with various polymeric resin materials conventionally used as a combined use material of adsorption agent. Specifically, for example, when applied to an adsorbent in which an active ingredient is dispersed in a polymer resin material, the silica gel of the present invention is added to the aforementioned polymer resin material (or a solution thereof) together with the active ingredient. The adsorbent can be obtained by dispersing the carrier silica gel to be finely divided by a conventionally known method such as spray drying. At this time, since the carrier silica gel of the present invention can be uniformly dispersed in the polymer resin material (or solution thereof) due to its pore characteristics and the like, a stable quality adsorbent can be obtained.

  The use form of the adsorbent of the present invention prepared in this way is not particularly limited, and depending on the purpose, it can be used as it is, or can be molded into an appropriate shape according to the use method of other adsorbents, or can be ventilated / passed through. It can be used as appropriate by enclosing it in an aqueous / oil-permeable container.

  Since the adsorbent of the present invention uses the carrier silica gel having the above-mentioned advantages and supports the supported components such as various active ingredients in the pores, the conventional adsorbent using the conventional porous carrier such as silica gel is used. Compared with the adsorbent, it is possible to more accurately control various adsorption performances such as the selectivity of the object to be adsorbed, the adsorption speed, and the change over time in the adsorption amount. Compared to conventional adsorbents, more active components can be supported on the carrier silica gel, and since the silica gel and supported components are less modified and deteriorated, a stable adsorption effect can be obtained over a long period of time. It is considered a thing.

  Substances adsorbed and removed by the adsorbent of the present invention include ammonia and various amine-based nitrogen-containing compounds, sulfur-containing compounds typified by mercaptans, and various aldehydes, organic acids, esters, various dienes, Examples thereof include organic compounds such as aromatics, cigarette smoke, automobile exhaust gas, and heavy metal compounds in gases and liquids used in factories and the like. These adsorbents may be present alone or as a mixture, and it is also assumed that various third components coexist.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention can be arbitrarily changed and implemented in the range which does not deviate from the summary, without being restrict | limited to a following example.

(1) Analysis method of carrier silica gel:
(1-1) Pore volume, specific surface area:
The BET nitrogen adsorption isotherm was measured with AS-1 manufactured by Cantachrome, and the pore volume and specific surface area were determined. Specifically, the pore volume adopts a value when the relative pressure P / P ₀ = 0.98, and the specific surface area is nitrogen at three points of P / P ₀ = 0.1, 0.2, 0.3. It calculated using the BET multipoint method from the adsorption amount. Further, the pore distribution curve and the differential pore volume at the mode diameter (D _max ) were determined by the BJH method. The interval between each point of the relative pressure to be measured was 0.025.

(1-2) Powder X-ray diffraction:
Using a RAD-RB apparatus manufactured by Rigaku Corporation, measurement was performed using CuKα as a radiation source. The divergence slit was ½ deg, the scattering slit was ½ deg, and the light receiving slit was 0.15 mm.

(1-3) Content of metal impurities:
Hydrofluoric acid was added to 2.5 g of the sample and heated to dryness, and then water was added to make 50 ml. ICP emission analysis was performed using this aqueous solution. Sodium and potassium were analyzed by flame flame light method.

(1-4) Solid Si-NMR measurement:
Conditions of CP / MAS (Cross Polarization / Magic Angle Spinning) probe using a Bruker solid-state NMR device (“MSL300”), a resonance frequency of 59.2 MHz (7.05 Tesla), and a 7 mm sample tube Measured with Specific measurement conditions are shown in Table 1 below.

Analysis of measured data (Q ⁴ Determination of the peak position) is performed by a method of extracting each peak by the peak division. Specifically, waveform separation analysis using a Gaussian function is performed. For this analysis, waveform processing software “GRAMS386” manufactured by Thermogalatic can be used.

(2) Production and evaluation of carrier silica gel:
-Examples 1-3:
1000 g of pure water was charged into a 5 L separable flask (with a jacket) made of glass and fitted with a water-cooled condenser open to the atmosphere at the top. While stirring at 100 rpm, 1400 g of tetramethoxysilane was charged into this over 3 minutes. The water / tetramethoxysilane molar ratio is about 6. Warm water at 50 ° C. was passed through the jacket of the separable flask. Stirring was continued, and the stirring was stopped when the contents reached the boiling point. Subsequently, hot water of 50 ° C. was passed through the jacket for about 0.5 hour to gel the sol produced. Thereafter, the gel was quickly taken out and pulverized through a nylon net having an opening of 600 microns to obtain a powdery wet gel (silica hydrogel). 450 g of this hydrogel and 450 g of pure water were charged into a 1 L glass autoclave. The conditions were 130 ° C. × 3 Hr for Example 1, 150 ° C. × 3 Hr for Example 2, and 200 ° C. × 3 Hr for Example 3. Hydrothermal treatment was performed. After hydrothermal treatment for a predetermined time, no. It filtered with 5A filter paper, and it dried under reduced pressure until it became constant weight at 100 degreeC, without washing the obtained silica gel with water. After drying, the mixture was pulverized in a mortar and classified by a sieve to obtain a silica gel powder having an average particle size of 10 μm. These are the carrier silica gels of Examples 1 to 3, respectively.

Various physical properties of the obtained carrier silica gel of Examples 1 to 3 are shown in Table 2. In any silica gel, no peak on the low angle side (2θ ≦ 5 deg) due to the periodic structure is observed. The impurity metal contents of the carrier silica gels of Examples 1 to 3 were 0.2 ppm sodium, 0.1 ppm potassium, 0.2 ppm calcium, and no other metals were detected. In addition, the chemical shift value δ of the Q ⁴ peak of solid-state Si-NMR is smaller than the value calculated by the left side {−0.0705 × (D _max ) −11.36} of the above-described formula (I). It became a value (a value existing on the more negative side).

Reference examples 1 and 2:
Silica gel CARIACT G-6 manufactured by Fuji Silysia Chemical Co., Ltd. was used as the carrier silica gel of Reference Example 1, and the same CARIACT G-10 was used as the carrier silica gel of Reference Example 2. Their physical properties are shown in Table 2 below. According to the powder X-ray diffraction pattern, no peak on the low angle side due to the periodic structure is observed in any of the carrier silica gels of Reference Examples 1 and 2. Further, the chemical shift value δ of the Q ⁴ peak of the solid Si-NMR is larger than that of any of the carrier silica gels of Reference Examples 1 and 2, and the formula (I) described above. The value was larger than the value calculated from {−0.0705 × (D _max ) −11.36} on the left side of (the value existing on the plus side). That is, it is judged that the carrier silica gels of Reference Examples 1 and 2 are more distorted in structure than the carrier silica gels of Examples 1 to 3, and are susceptible to changes in physical properties.

-Underwater thermal stability test of carrier silica gel:
Pure water was added to each of the carrier silica gels of Examples 1 to 3 and Reference Examples 1 and 2 to prepare a 40 wt% slurry. About 40 ml of the slurry prepared above was sealed in a stainless steel microbomb having a volume of 60 ml, and immersed in an oil bath at 280 ± 1 ° C. for 3 days. A part of the slurry was extracted from the microbomb and filtered through 5A filter paper. The filter cake was vacuum dried at 100 ° C. for 5 hours. The results of measuring the specific surface area of this sample are shown in Tables 2 and 3. The carrier silica gels of Examples 1 to 3 were less reduced in specific surface area and superior in hydrothermal stability than the carrier silica gels of Reference Examples 1 and 2.

  From the results in Table 2, it can be seen that the carrier silica gels of Examples 1 to 3 have a sharper and more controlled pore distribution than the conventional carrier silica gels represented by Reference Examples 1 and 2. I understand. Therefore, when used as an adsorbent, by appropriately controlling the pore size according to the molecular size of various substances (active ingredients) supported in the pores, the target adsorbent can be selected selectively. It is thought that it can be adsorbed at an arbitrary speed.

  In addition, the carrier silica gels of Examples 1 to 3 are less homogeneous than metal oxides of the conventional carrier silica represented by Reference Examples 1 and 2 and have a much higher purity and less distortion of the siloxane bond angle. Since it has a stable structure, it is understood that the reactivity is low, the heat resistance and the water resistance are excellent, and the change in physical properties such as pore characteristics is small even under severe use conditions. Therefore, when used as an adsorbent, it does not exhibit unnecessary activity with respect to the loaded active ingredient, and can stably carry various drugs, etc., and even when used in combination with highly active ingredients, it does not denature or deteriorate. It is considered difficult to occur.

  Therefore, the carrier silica gels of Examples 1 to 3 are adsorbents using conventional carrier silica gels typified by Reference Examples 1 and 2 when various active ingredients are supported as supported components and used as adsorbents. In comparison, it is presumed that better adsorption performance can be obtained.

  Although the carrier silica gels of Examples 1 to 3 were obtained as crushed and crushed particles, they were molded into other shapes (for example, spherical, tablet-like, extruded products, pellets, etc.) by a known molding technique. Also good.

(3) Production of adsorbent:
The carrier silica gels of Examples 1 to 3 can adsorb the substances desired to be adsorbed selectively and at a desired adsorption rate by carrying various active ingredients and the like (adsorbents of Examples 1 to 3). Can be used as The type of active component to be supported, the state of being supported, and the method of supporting are as described in detail above.

As a specific example 1, the carrier silica gel of Example 1 was impregnated with copper sulfate to prepare an adsorbent. First, copper sulfate was dissolved in water to a concentration of about 10% by weight, and 10 g of the carrier silica gel of Example 1 was added to 50 cc of this solution and stirred, followed by filtration to remove water to dryness, and support for CuSO ₄ Silica gel (adsorbent of Example 1) was obtained. When the weight increment of the silica gel after loading with respect to before loading of copper sulfate was measured and the amount of copper sulfate impregnation of the adsorbent of Example 1 was determined based on this, it was about 7% by weight.

  As a specific example 2, 20 g of 3-aminopropyltriethoxysilane was added to 20 g of the carrier silica gel of Example 1 in a toluene solvent, and heated and refluxed for 15 hours to prepare a new adsorbent. After heating to reflux, the mixture was filtered, washed with toluene and acetone, and then dried to obtain 3-aminopropyl group-supporting silica gel (adsorbent part 2 of Example 1). When the supported amount of 3-aminopropyl group was determined by elemental analysis of N, the supported amount of 3-aminopropyl group in “Adsorbent 2 of Example 1” was about 1.7 mmol / g.

(4) Adsorbent performance evaluation:
Various performances of the adsorbents of Examples 1 to 3 can be evaluated by, for example, the following methods.

<Evaluation of loading amount of active ingredient>
In addition to the increase in weight before and after loading, when the active ingredient to be supported is an organic substance, a method in which weight loss by thermogravimetric analysis is used as a guideline of the loading amount, Re-extraction, titration method, absorptiometry, gas chromatography, liquid chromatography, infrared absorption spectroscopy, NMR method, etc., titration method, total carbon content There are methods such as quantification by analytical methods and various spectroscopic methods. In the case of an inorganic substance, an atomic absorption analysis method or an atomic emission analysis method dissolved in an HF solution or the like is also preferably used.

<Adsorption performance evaluation>
As a simple evaluation method when an adsorbed substance component is present in a liquid or gas, an adsorbent carrying an active ingredient is filled in, for example, a glass column, and the liquid or gas (according to actual use conditions) is fixed at a constant speed. (Select similar conditions such as temperature, pressure, etc.) and distribute the concentration of the adsorbed components not adsorbed by total carbon analysis, titration, absorptiometry, gas chromatography, liquid chromatography, infrared A method of tracking over time by absorption spectroscopy, NMR, etc., or immersing the adsorbent carrying the active ingredient in a liquid or gas in an environment similar to the actual use conditions in a glass beaker or flask There is a method of keeping the temperature and tracking the concentration of the adsorbed component in the liquid or gas over time by the above analysis method.

  In a system in which an adsorbed component is present in a gas, a method for tracking the weight increase of the adsorbent with time is also simple.

  Since the types and usage forms of the active ingredients supported by these adsorbents are various, if simple evaluation is difficult, the adsorbent is subjected to actual use conditions, and the adsorption performance is evaluated for actual use effects in each application. As a direct observation method (sensory evaluation by human nose and mouth, safety evaluation using animals and plants, sustainability of antibacterial performance), and the like. These various evaluation methods are appropriately selected according to the purpose of evaluation and the type of adsorbent to be evaluated.

  Since the adsorbents of Examples 1 to 3 use the carrier silica gel of Examples 1 to 3 having the above-described advantages and have various active components supported in the pores, the selectivity and adsorption rate of the adsorbed substance When the various adsorption performances such as the adsorption period and the amount of adsorption over time are evaluated, the adsorption is more controlled than the conventional adsorbent, for example, the adsorbent using the carrier silica gel of Reference Examples 1 and 2. It is considered that the accurate adsorption performance can be obtained and the adsorption performance can be obtained stably over a long period of time.

  The carrier silica gel of the present invention is easier and cheaper to produce than the conventional carrier silica gel, has a wide range of choices for the types of active ingredients that can be supported and the size of the molecules, and a large amount of these. It can be supported. In addition, since the impurity metal content is low and the purity is high, there is little risk of damaging the supported active ingredient. In addition, it is excellent in water resistance, heat resistance, long-term physical property stability, and the like.

  Therefore, the adsorbent of the present invention obtained by using it is easier and cheaper to produce than conventional adsorbents, and has a range of choices for the types of active ingredients that can be supported and the size of the molecules. It is wide and can carry a large amount of these. In addition, the adsorption performance can be controlled more precisely, and a stable adsorption effect can be obtained over a long period of time. Therefore, the adsorbent of the present invention can be suitably used in the conventional various adsorbent fields described above, and the industrial applicability is extremely high.

Claims (8)

An adsorbent comprising silica gel satisfying the following (a) to (g).
(A) The pore volume is 0.05 ml / g or more and 3.0 ml / g or less.
(B) The specific surface area is 100 m ² / g or more and 1500 m ² / g or less.
(C) The most frequent pore diameter (D _max ) is less than 35 nm.
(D) The volume of pores having a diameter in the range of D _max ± 20% is 50% or more of the total pore volume.
(E) It is amorphous.
(F) The total content of metal impurities is 500 ppm or less.
(G) When the chemical shift of the Q ⁴ peak in solid Si-NMR is δ (ppm), δ satisfies the following formula (I).
−0.0705 × (D _max ) −11.36> δ Formula (I) 2. The adsorbent according to claim 1, wherein the differential pore volume at the most frequent pore diameter (D _max ) of the silica gel is 2 ml / g or more and 20 ml / g or less. The adsorbent according to claim 1 or 2, wherein a value of Q ⁴ / Q ³ peak in solid-state Si-NMR measurement of silica gel is 1.3 or more. The adsorbent according to any one of claims 1 to 3, wherein the silica gel is produced through a step of hydrolyzing silicon alkoxide. The adsorbent according to any one of claims 1 to 4, wherein a substance that interacts with an adsorbed substance is supported in the pores of silica gel. Substances that interact with the adsorbents are: cormorant, cormorant, fern, bay, jasmine, cinnamon, clove, eucalyptus, bergamot, dokudami, abies, bamboo, cormorant, cypress, hiba, pine, cormorant, cypress, rose, holly And an extract of at least one plant selected from the group consisting of: Willow, Kiri, Quercus, Forsythia, Lilac, Citrus, Peppermint, Apple, Persimmon, Plum, Peach, Daikon, Radish, Kaiware, Persimmon, Shiso, and Aloe The adsorbent according to claim 1, wherein the adsorbent is characterized. The substance that interacts with the object to be adsorbed is at least one compound species selected from the group consisting of compound species having any metal element of Cu, Zn, Sn, Pb, Ti, Zr, Al, and Fe. The adsorbent according to any one of claims 1 to 6, wherein the adsorbent is characterized by that. The adsorbent according to any one of claims 1 to 7, wherein a part or all of hydroxyl groups remaining in the silica gel are converted into a group containing S or N by a coupling treatment. .